Azo dyestuffs



selected from the particular success on Patented Nov. 1, 1938 UNITED STATES PATENT OFFICE 2,134,728 AZO nms'rurrs Heinrich Morschel, Cologne-Deutz, and Otto Goll, Leverknsen I. G.-Werk, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation ,of Delaware No Drawing.

6 Claims.

The present invention relates to water insoluble azo-dyestuffs and to a process of preparing same, more particularly it relates to water insoluble azodyestuffs which may be represented by the following general formula:

In the said formula X stands for a member group consisting of hydrogen, alkyl and aryl, R and R', stand for radicals of diazotization components free from solubilizing groups, and n stands for and 2. I

Our new dyestuffs are obtainable by coupling suitable diazo compounds with 4-arylazo-1-amino-l-hydroxynaphthalene or their N-alkyl or N- E dark brown to black shades.

The following examples illustrate the invention:

Example 1 .Cotton fiber is slop-padded with the following grounding solution: 3 parts by weight of 4(2'- inethoxy)-benzeneazo 1-amino- 7 -hydroxynaphthalene are stirred into a mixture of 3 parts by weight of water, 6 parts by weight of alcohol and 1.5 parts by weight of an aqueoussolution of caustic soda of 38 B., and the whole is made up to 1 'liter with a solution containing per liter 10 cos. of

an aqueous solution of caustic soda of 38 B., .10 cos. of purified sulfite cellulose waste liquor and 1 g. of the sodium salt of polyisobutylnaphthalene one of the numbers 1 r Application July 28, isssgseriai In Germany August 16, 1935 sulfonic acid. Development is effected with 1 liter of a diazo solution produced in the known manner from 1.75 gs. of 2-nitro-4-anisidine. After the dyeing has been soaped at the boil, an olive grey issobtained.

The dyestuff corresponds to the following formula:

NO: HIN N=NOCH1 N=N OClIs Example 2 Cotton is printed with a paste produced as follows: 4

Amixture of 4-(2'- chloro) benzene-azo-1-amino-7-hydroxynaphthalene gs The'diazoamino compound from diazotized 4-chloro-2-anisidine and sarcosine gs 3 An aqueous solution of caustic soda of 38 B ccs.. 3 Glycolmonomethyl ether ccs.. I 5 Neutral starch tragacanth paste gs 50 is made up with water to gs. After an intermediate drying, development is effected with acid steam, and then the dyeing is soaped at the boil. A black shade is obtained.

mula

The dyestuff corresponds to the following for- Example 3 When in the printing paste of Example 2 there is used the diazoamino compound from diazotized 4-chloro-2-toluldlne and sarcosine, a saturated dark brown is obtained.

"flhe dyestuff corresponds to the following form a:

Example 4 100 gs. Cotton is printed with this paste. After drying the print is steamed for 5 minutes with steam-containing acetic acid. Then the material is rinsed, soaped at the boil, again rinsed and dried. A deep black shade is obtained.

l'ghe dyestuff has the probable following form a:

In the following table there are given further combinations prepared in accordance with the 2.5 gs. of the diazoamino compound, which present process and their shades on cotton:

Coupling component Diazo component Shade on cotton 4(1-methyl-5 chlotophenylezo)-l-amino-7-hydroxynaph- 2-nitro-4-chlorauiiine Olive-brown.

n '4nitro-4-nmino-2,5-dimethoxyazobenzene Blackish brown.

D 3-chloraniline Greyish brown. (T-mthoxy-iV-chlorophenylaw)-1-amino-7-hydroxynapb- 2,6-dichloroaniiine Brown-olive.

Dn 2-chloro-a-methoxy-4-ben1.oylamino-i-aminoben- Blackish brown.

' zene. 4(2'-methoxy-5-chloro-l-emino-7-hydroxy-uaphthslene.. 4-nitro-2-amino-l-methylbenzene Olive-brown. (T-nitrophenylnao)-l-amino-7-hydroxy-naphthalene.. kchloro-2amino-1-methoxybenzene. Brownian black,

Do b-nitro-2-emino-l-methoxybenzene... Greenish black.

Dc 4-chloro-3-amino-1-triiiuoromethylbe Reddish hlack brown. 4(2'-chlorophenyluo)-1-am1no-7-hydroxynaphthalene....-- 3-chioreniline Greenisb black brown.

Do i-chloro-z-amino-l-methoxybenzen Bluish dark brown.

D I l-aminonnthraquinone Dark brown. 4(2'-methoxyphenylar.o)-l-emino-7-hydroxynaphthalene 2 ,3-dirnethyl-4-aminoazoben1-en Brownish olive.

2.5-dichloraniline Do. 4(fiitro-fl-methyipbenylazo-1-amino-7-hydroxynephtha- Itchlorauiline Dark brown.

e. 4(7-methoxyphenylazo)-1amin0-7-hydr0xynaphthalene B-amino-l-chiom-l-trifluormethylbenzene Bleckish brown. fiitro-f-methylphenylaw-l-amino-7-hydroxynephths- 5-cliloro-2-nminol-methylbenzcne Do.

D 4-chl0ro-2-amino-1-metl1oxybcnzene Do. 4(1-nitm-4'-metboxyphenylaz0)-1-emino-7-hydroxynsph- 4-chloro-2-amino-1-metl1ylbenzene Do.

timiene. Y 2(2-nitn 4'-methoxypbenylam)-1-amino-7-hydroxynaph- 4(1-nino-4'-methoxyphenyluo)-1-amino-7-hydmxynaph- 5-nitm-2-emino-l-methoxybenwne 5-chloro-2-amino-1-metl1ylbenzeue..;

5-nitro-2-emino-1-methylbenzene Greenish black brown;

Blackish brown.

Olive dark brown.

thalene. 4(7'-hydxoxynaphthyl-(l) -ezo) l -emlno- 7 -hydroxynaphthabne.

. D0 4(2' nltmphenylazo) 1 methylamino 7 hydroxynaplithulene. J

4-nitzo-l-amino-benzene 2-aminodiphenyl-sulione 5-chloro-2 -amino-l-methylbenzene Do. Yellowish dark brown.

4-chloro-2-amino-1-methoxybenzen Black.

5-chl0ro-2'emino-i-methylbenzone Blackish brown.

l-chlom-2-amino-l-methoxybenzene Greeuisli black.

Brown.

4(3' henylsso)-1-etbylamino-Whydroxynaphthaleue. ine Dark olive brown. 4(1-nitrop euyluo)-l-etbylamino-7-hgdmgnnphthalene. Greenisb black. fli nitrophenylam)-1-phenylamino- -lzy roxynaphtlm- 2,5-dichlor'aniline Olive brown.

0. Do a 4-nitmniline Olive. 4(4' nitropheuylaso) 1 (4" methoxyphenylamino) 7 6-11itm-i-amino'l-methoxybenzene Greenish blackish brown.

hydmxymphtlnlene.

D 2,5-dichloraniline Blackish brown. D0 4-nitrsnili Ycllowlsh dark brown.

is obtainable from diaz otized 4,4'-dia.mino-3,3'- dimethcxydiphenyl and sarcosine (=1/200 mol) and 3.1 gs. or 4(2'-nitrophenylazo)-1-amino-7- hydroxynaphthalene (=1/200 mol) are stirred into a paste with the aid of a small quantity of water and dissolved by adding 3.0 com. of caustic soda solution of 38' B6. and 5.0 ccm. of glycolmonoethylether while slowly heating. The solution is added to a neutral starch tragacanth paste while stirring and filled up with waterto We claim: 1. Water insoluble azodyestufis of the general formula:

x l I wherein X stands for a member selected from the group consisting of hydrogen, alkyl and aryl, R and R" stand for diflerent radicals of diazotization components free from solubilizing groups, and n stands for one of the numbers 1 and 2, yielding when produced on the vegetable fiber in general brown to dark shades.

2. A water insoluble azodyestuif of the formula NH, N02

| OH OCH:

yielding when produced on the vegetable fiber deep black shades.

insoluble azodyestufls which comprises combinsolubilizing groups derived from an amine selectthe group consisting of hydrogen, alkyl and "aryl,

amines and amino azo compounds with a compound of the general formula:

R'--N=N wherein X stands for a member selected from the group consisting of hydrogen, alkyl and aryl, R stands for the radical of a diazotization com-' ponent free from solubilizing agroups, yielding when produced on the fiber in general brown to dark brown to black shades.

6. The process for the manufacture of watering on the fiber a diazo compound free from ed from the group consisting oi. monamines, diamines and amino azo compounds with a compound of the general formula:

RN=N wherein X stands for a member selected from R stands for a radical of the benzene series free from solubilizing groups, yielding when produced on the fiber in general brown to dark brown to black shades.

HEINRICH MORSCHEI... O'I'I'O GOLL. 

